JPH11109541A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material by which the sensitive material has a fine silver tone, is excellent in dryability and ensures little unevenness in gloss even after rapid processing. SOLUTION: A silver halide photographic sensitive material obtd. by disposing hydrophilic colloidal layers including a silver halide emulsion layer on a substrate is processed with a developing soln. contg. 5-20C saccharides having 5-20 hydroxyl groups and 5-20 carbon numbers. At least one of the hydrophilic colloidal layers has been hardened with a hardening agent represented by formula [where R<1> and R<2> are each H atom, an alkyl or aryl group or groups forming a heterocyclic ring together with an N atom by bonding to each other, R<3> is a substituent, (m) is 0-5, (1) is 0 or 1, X is an ion required to compensate an electric charge of each molecule and (n) is a number required to neutralize all the electric charges of each molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION There is a high demand for rapid processing of silver halide photographic light-sensitive materials, and particularly in the processing of medical silver halide photographic light-sensitive materials. recent years,
In healthcare, the number of test items has increased to improve diagnostic accuracy,
As a result, the number of radiographs has increased, and
From the necessity of prompt diagnosis in emergency medicine, speeding up of development processing is strongly desired.

In order to achieve rapid processing, it is first necessary to increase the activity of a developing solution in order to obtain the same image density as in ordinary processing.

However, generally speaking, when the activity of the developer is increased, it becomes difficult to suppress the elongation of the developed silver filament during the development, which causes deterioration of the silver tone. Furthermore, in order to obtain a safe environment, without using hydroquinones harmful to the human body, JP-A-7-77781, using reductones as a developing agent as disclosed in JP-A-7-110554 and the like In this case, the silver tone is remarkably deteriorated.

On the other hand, in order to achieve rapid processing, it is necessary to improve the drying ability of an automatic processor or the drying property of a photosensitive material.

[0006] In order to improve the drying property of the photosensitive material, it is necessary to reduce the amount of binder. However, when the amount of binder is reduced, fog failure occurs due to external pressure received during processing or handling.

Also, instead of reducing the amount of binder,
Increasing the amount of the hardener added to the protective layer of the photosensitive material to reduce the amount of water contained in the photosensitive material during processing also contributes to the improvement of the drying property. If a hardener such as is used, uneven gloss is generated after the treatment.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which has an excellent silver tone, has excellent drying properties, and has little gloss unevenness even when subjected to rapid processing. Is to provide a way.

[0009]

The above object of the present invention is achieved by the following constitution. (1) A method for processing a silver halide photographic light-sensitive material comprising a support provided with a hydrophilic colloid layer including a silver halide emulsion layer with a developer, the method comprising the steps of: Wherein at least one layer of a hydrophilic colloid layer containing is hardened with a hardener represented by the following general formula (1), and the developer is a saccharide having 5 to 20 carbon atoms and 5 to 20 hydroxyl groups. A method for processing a silver halide photographic light-sensitive material, characterized in that the developer is a developer.

[0010]

Embedded image[Wherein, R¹ , R^Two Represents a hydrogen atom, an alkyl group, an aryl
Group or R¹ , R^Two Are bonded to each other and
Represents a group forming an elementary ring.

R^Three Represents a substituent. m represents 0 to 5
And when m is 2 or more, a plurality of R^Three Is the same
They may be different from each other. 1 represents 0 or 1.

X represents an ion necessary to cancel the electric charge of the molecule. n represents the number required to neutralize the total charge of the molecule. However, when an inner salt is formed, 0
It is. (2) The method for processing a silver halide photographic material as described in (1) above, wherein the developer is a developer containing reductones.

Hereinafter, the present invention will be described in detail. The silver halide photographic material (the silver halide photographic material of the present invention) used in the processing method of the silver halide photographic material of the present invention is a silver halide emulsion. Layer and a hydrophilic colloid layer that is not a silver halide emulsion layer, for example, at least one of a dye layer, a filter layer, an intermediate layer, and a protective layer.
The layer is hardened with a hardener represented by the general formula (1).

[0014]

Embedded image[Wherein, R¹ , R^Two Represents a hydrogen atom, an alkyl group, an aryl
Group or R¹ , R^Two Are bonded to each other and
Represents a group forming an elementary ring.

R^Three Represents a substituent. m represents 0 to 5
And when m is 2 or more, a plurality of R^Three Is the same
They may be different from each other. 1 represents 0 or 1.

X represents an ion necessary to offset the electric charge of the molecule.
Indicates ON. n is required to neutralize the total charge of the molecule
Represents a number. However, when an inner salt is formed, 0
It is. -In the hardener represented by the general formula (1), R¹ , R^Two Is a table
Examples of the alkyl group include a methyl group, an ethyl group,
Benzyl group, phenethyl group, 2-ethylhexyl group, etc.
And as the aryl group, for example, phenyl
And naphthyl groups. Also, R¹ , R^Two But
As an example of a heterocyclic ring that forms a bond with a nitrogen atom
Is, for example, a pyrrolidine ring, a piperazine ring, morpholine
And the like. Also, R¹ , R^Two In addition,
Those having a group are also included. Examples of these substituents include
For example, alkyl group, halogen atom, sulfo group, phospho
Group, ureido group, alkoxy group, sulfooxy group
Can be

R^Three Are, for example, -N
R^Four R^Five (R^Four And R^Five Is R¹ , R^Two Is synonymous with ),Halo
Gen atom, carbamoyl group, sulfo group, ureido group,
Examples include a alkoxy group and an alkyl group. R_ThreeIs more
It may have a substituent, examples of these substituents
Represents a halogen atom, an alkyl group, a carbamoyl group,
An e-group, a sulfoxy group, a ureido group and the like can be mentioned.

[0018] Preferred examples of ion required to offset the charge of the molecule X represents a halide ion, sulfate ion, sulfonate ^{_{ion, C1O - 4, BF - 4}} ,
BF ^- _{6 and the} like. n represents a number necessary to neutralize the total charge of the molecule, and is usually 0 to 2. It is 0 when an internal salt is formed.

Hereinafter, specific examples of the hardener represented by the general formula (1) are shown, but the compound of the general formula (1) used in the present invention is not limited to these.

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

In the silver halide photographic light-sensitive material used in the processing method of the silver halide photographic light-sensitive material of the present invention, the silver halide composition of the silver halide emulsion layer may be arbitrarily selected, for example, silver chloride, silver iodochloride And any silver halide such as silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide and the like.

When the silver halide grains contain silver iodide, the content of silver iodide is preferably 1.5 mol% or less, more preferably 1.0 mol% or less, as the average silver iodide content.

The average grain size of the silver halide grains is 0.15 to 0.15.
5.0 μm, preferably 0.2 to 3.0 μm
Is more preferable, and most preferably 0.2 to
2.0 μm.

The crystal habit of the silver halide grains may be any crystal habit such as a cubic, octahedral, or twinned crystal, but is preferably a tabular silver halide grain.

Tabular silver halide grains are grains having two opposing parallel main planes, and may be either those having the (111) plane as the main plane or those having the (100) plane as the main plane. Good.

The tabular silver halide grains preferably used in the present invention have a ratio of the grain size to the grain thickness (hereinafter referred to as aspect ratio) of 2 or more, more preferably 2.0 or more, and 15 or more. It is less than 0. In particular, 3 or more, 10
Preferably it is not full. Here, the grain size means an average projected area diameter (hereinafter, sometimes simply referred to as a grain size), and is a circle equivalent diameter of a projected area of a tabular silver halide grain (the same projected area as the silver halide grain is defined as a circle). The diameter of the circle having The term "grain thickness" refers to the distance between two parallel main planes forming tabular silver halide grains.

The average grain thickness of the tabular silver halide grains is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.60 μm, still more preferably from 0.02 to 0.60 μm.
5 to 0.50 μm. Average particle size is 0.15 to 5.0
μm, more preferably 0.4 to 3.0 μm, and most preferably 0.4 to 2.0 μm.
m.

As the silver halide emulsion having tabular silver halide grains, a monodisperse emulsion having a narrow particle size distribution is preferable. Specifically, the width (%) of the particle size distribution = (standard deviation of particle size / Average particle size)
The width of the distribution defined by × 100 is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

A silver halide emulsion having tabular silver halide grains can also be prepared by the method described in US Pat. No. 5,320,938.

Nuclei are formed at a low pCl in the presence of iodide ions, and after nucleation, Ostwald ripening and / or growth are performed to obtain tabular silver halide grains having a desired grain size and distribution. .

In the tabular silver halide grains, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), and a rhodium salt (including a complex salt) are formed during the process of forming and / or growing the grain. ) And an iron salt (including a complex salt), and a metal ion is added thereto so that the metal element can be contained inside the particle and / or on the surface of the particle.

The tabular silver halide grains are preferably spectrally sensitized with a methine dye or the like. As the sensitizing dye, a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar dye, a hemicyanine dye, a styryl dye, a hemioxonol dye, and the like can be used. Particularly useful dyes are those belonging to cyanines, merocyanines and complex merocyanines.

As these dyes, any of nuclei generally used can be used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a nucleus in which a hydrocarbon ring is fused to these nuclei, that is, indolenine A nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be used. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or composite merocyanine dye, nuclei having a ketomethine structure include a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazoline-2,4-dione nucleus. 5, rhodanine nucleus, thiobarbituric acid nucleus, etc.
A 6-membered heterocyclic nucleus can be used.

These sensitizing dyes may be used alone or in combination, and the combination is often used for supersensitization. In addition to the sensitizing dye, a dye having no spectral sensitization itself or a substance which does not substantially absorb visible light but exhibits a supersensitizing effect when used together with the sensitizing dye may be used. Examples of these substances include a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group, an aromatic organic acid formaldehyde condensate, a cadmium salt, an azaindene compound, and the like.

The spectral sensitizing dye is preferably added as a dispersion of solid fine particles rather than as a solution in an organic solvent. In particular, it is preferable to disperse and add a solid fine particle dispersion substantially insoluble in water in an aqueous system substantially free of an organic solvent or surfactant. The particle size after dispersion is preferably 1 μm or less.

The silver halide emulsion used in the present invention can be subjected to chemical sensitization.

Chemical sensitization includes a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, a reducing substance, A reduction sensitization method using gold, a noble metal sensitization method using a noble metal, or the like can be used alone or in combination. Among them, a sulfur sensitization method,
Selenium sensitization, tellurium sensitization, reduction sensitization, and the like are preferable, and these sensitizations are also preferably used in combination.

Specific examples of the sulfur sensitizer include thiosulfates such as sodium thiosulfate, 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea. Preferred examples include thiourea derivatives, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and simple sulfur. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Specific examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc.
It is preferably from 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁹ mol per mol. More preferably, 1 × 10 ^-4 mol to 1 × 1
0 ^-6 mol.

The sulfur sensitizer and the gold sensitizer may be dissolved in water or alcohols or other inorganic or organic solvents and added to the silver halide emulsion in the form of a solution. Alternatively, it may be added to a silver halide emulsion in the form of a dispersion obtained by emulsification and dispersion using a medium such as gelatin. Both sulfur sensitization and gold sensitization may be performed simultaneously, or separately and stepwise. In the latter case, favorable results may be obtained if gold sensitization is performed after or during sulfur sensitization appropriately.

Reduction sensitization is performed by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion so that the sensitization is performed during the growth of the silver halide grains of the silver halide emulsion. . Preferred examples of the reducing agent used for reduction sensitization include thiourea dioxide, ascorbic acid, and derivatives thereof. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylaminoboranes, sulfites and the like.

Examples of the selenium sensitizer include colloidal selenium metal, isoselenocyanates (for example, allyl isoselenocyanate, etc.), and selenoureas (for example,
N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylselenourea, N, N, N'-trimethyl-N'-hepta Fluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N , N-
Dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), Selenides (for example, triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.) are exemplified. Particularly preferred selenium sensitizers are selenides, selenoureas, selenamides, and selenium ketones.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 1 per mol of silver halide.
It is about ^0-4 mol.

The chemical ripening using a selenium sensitizer is preferably performed at a temperature in the range of 40 to 90 ° C., more preferably 45 ° C. or more and 80 ° C. or less. The pH of the emulsion
Is preferably in the range of 4 to 9, and pAg is preferably in the range of 6.0 to 9.5.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-).
Dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride,
Butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates. The technology for using the tellurium sensitizer is the same as the technology for using the selenium sensitizer. In the present invention, chemical sensitization may be performed by combining selenium sensitization and tellurium sensitization.

The conditions of the chemical ripening step, for example, pH, pA
There are no particular restrictions on g, temperature, time, and the like, and the reaction can be performed under conditions generally performed in the art.

Various photographic additives can be added to the emulsion of the silver halide photographic light-sensitive material before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, Research Disclosure (hereinafter referred to as R).
It is called D. ) No. 17643 (December 1978),
RDNo. 18716 (November 1979) and RDN
o. 308119 (December 1989). These three R
The types and locations of the compounds described in D are described below.

[0054]

[Table 1]

As the support of the silver halide photographic light-sensitive material, those described in the above RD can be mentioned. A suitable support is a polyethylene terephthalate film or the like, and the support surface may be provided with an undercoat layer to improve the adhesion to the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

Next, the developing solution (the developing solution of the present invention) used in the method for processing a silver halide photographic material of the present invention will be described.

The developing solution (developing solution of the present invention) used in the method for processing a silver halide photographic light-sensitive material of the present invention is:
It contains a saccharide having 5 to 20 carbon atoms and 5 to 20 hydroxyl groups (the saccharide of the present invention).

The following are specific examples of the saccharide of the present invention which is preferable to be contained in the developer of the present invention, but the saccharide used in the present invention is not limited to these saccharides. A-1: D-trait A-2: L-trait A-3: meso-trait A-4: adunit A-5: D-arabit A-6: L-arabit A-7: adunit A-8: xylit A-9: D-Sorbit A-10: L-Sorbit A-11: D-Mannit A-12: D-Edit A-13: D-Tallit A-14: Dulcit A-15: Alit A-16: Persett A-17: Borremit A-18: β-sedoheptite A-19: meso-inosit The saccharides of the present invention may be used alone or in combination of two or more.

As the developing agent used in the developing solution, any commonly used developing agent can be used, but in the present invention, it is preferable to use retacticones.

Reductones preferably used in the developer of the present invention are compounds represented by the following formula (D).

[0061]

Embedded image [Wherein, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. R ₁ and R ₂ are R ₁ and R ₂
And may combine with each other to form a ring.
X represents -CO- or -CS-, and k represents 0 or 1.
Represents

M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group. As the reductones of the present invention used in the developer of the present invention, among the compounds represented by the general formula (D), R ₁ and R ₂
Is bonded to each other to form a ring, and is represented by the following general formula (Da)
The compound represented by is preferred.

[0063]

Embedded image [Wherein R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, an amide Represents a group or a sulfonamide group.

Y ₁ represents an oxygen atom or a sulfur atom,
Y ₂ represents an oxygen atom, a sulfur atom or a ＮＲNR ₄ group. R
₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

[0065] M _1, M ₂ are each synonymous with M _1, M ₂ of the general formula (D). In the general formula (D) or the general formula (Da), the alkyl group is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group Alternatively, an amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group. Each of these groups may have a substituent, and the substituent is preferably a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group, or the like.

As M ₁ and M ₂ , a hydrogen atom and a sodium atom are preferable.

Specific examples of the compound represented by formula (D) or (Da) which can be used in the present invention are shown below, but the compounds which can be used in the present invention are not limited to these. It is not something to be done.

[0068]

Embedded image

[0069]

Embedded image

The above compounds are typically ascorbic acid, erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by known synthesis methods.

A preservative, a buffer, a development accelerator, and an antifoggant can be added to the developer of the present invention.

As a preservative that can be used, a sulfite can be used. Alternatively, an organic reducing agent can be used.

Examples of buffers that can be used include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, and potassium borate. , Sodium tetraborate, potassium tetraborate, o
Sodium-hydroxybenzoate, potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate, potassium 5-sulfo-2-hydroxybenzoate, and the like.

Examples of development accelerators that can be used include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, and other 1-phenyl-3 compounds. -Pyraziridones, hydrazines, imidazoles.

The antifoggants which can be used include alkali metal halides such as potassium iodide and organic antifoggants. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl- Examples thereof include nitrogen-containing heterocyclic compounds such as benzimidazole, 2-thiazolylmethyl-benzimitazole, indazole, hydroxyazaindolizine, and adenine, and 1-phenyl-5-mercaptotetrazole.

In addition to the developing solution, a bisulfite adduct of a chelating agent or a hardening agent can be added, and it is also preferable to add a silver sludge inhibitor. It is also preferable to add a cyclodextrin compound.
The compound described in JP-A No. 3 is particularly preferred. An amine compound can be added to the developer, and for example, compounds described in US Pat. No. 4,269,929 are particularly preferable.

Further, if necessary, methyl cellosolve,
Methanol, acetone, dimethylformamide, cyclodextrin compounds and the like can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

In the present invention, it is also preferable to add a starter to the developer prior to processing. As a starter,
In addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

For fixing, a known fixing solution can be used. A fixing agent, a chelating agent, a pH buffer, a hardening agent, a preservative, and the like can be added to the fixing solution, and examples thereof include JP-A-4-242246 (page 4) and JP-A-5-246.
JP-A-113632 (pages 2 to 4) can be used. In addition, known fixing accelerators can be used.

In the processing method of the silver halide photographic light-sensitive material of the present invention, the steps from development to drying are carried out in an automatic developing machine in 15 steps.
It is suitable for processing to be completed within seconds to 120 seconds. That is, the time from when the leading end of the photosensitive material starts to be immersed in the developing solution to when the leading end comes out of the drying zone through a processing step (so-called Dry to Dry time).
Is suitable for processing performed within 15 seconds to 120 seconds. More suitable Dry to Dry processing time is 15 seconds to
Within 90 seconds.

The development time is 3 to 40 seconds, preferably 6 to 40 seconds.
It takes 20 seconds. The development temperature is 25 to 50C, preferably 30 to 40C. The fixing temperature is about 20 to 40C, preferably 29 to 37C, and the fixing time is 3 to 30 seconds, preferably 4 to 20 seconds.

The drying step is performed in a drying zone provided in an automatic developing machine, which is usually blown with hot air at 35 to 100 ° C., preferably 40 to 80 ° C., or provided with heating means by far infrared rays.

As an automatic developing machine, an automatic developing machine equipped with a mechanism for applying water or an acidic rinsing liquid having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps (JP-A-3-264953) Publication). Further, the automatic developing machine may have a built-in device capable of adjusting a developing solution and a fixing solution.

In the method for processing a silver halide photographic light-sensitive material of the present invention, the processing is preferably carried out at a replenishment rate of 180 ml / m ² or less, more preferably from 8 to 160 ml.
/ M ² , particularly preferably 10 to 100 ml / m ² .

[0085] The replenishment rate of the fixing solution is preferably 180 ml / m ² or less, more preferably at 8~160ml / m ^2, it is preferred in particular 10 to 100 ml / m ^2.

To carry out the processing method for a silver halide photographic light-sensitive material of the present invention, a developing solution, a replenishing developer, a starter, a fixing solution, a replenishing fixing solution and the like are mixed with a solid processing agent such as
It is preferable to use a treatment liquid prepared using tablets.

The solid processing agent is formed by kneading a thick liquid or fine powder or granular photographic processing agent and a water-soluble binder, and molding the photographic processing agent. Can be obtained by employing any means such as forming (See, for example, JP-A-4-29136, JP-A-4-85535, JP-A-4-85536, JP-A-4-85533, JP-A-4-85534, JP-A-4-72341, etc.).

As a preferred method for producing a tablet, there is a method in which a powdered solid processing agent is granulated and then subjected to a tableting step to form the tablet. By doing so, there is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a tablet formed by a tableting step by simply mixing a solid processing component.

[0089]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 <Preparation of Seed Emulsion 1> JP-B-58-58288, 58-58289
The following solution B1 and the following solution C1 were each added to the following solution A1 prepared at 42 ° C. by a simultaneous mixing method by 464.3 ml by a simultaneous mixing method using a mixing stirrer described in the above-mentioned publication for 1.5 minutes. And nucleation.

After stopping the addition of the solution B1 and the solution C1, the temperature was raised to 60 ° C. over a period of 60 minutes, and
After adjusting the pH to 6.0 with% KOH, the solution B1 and the solution C1 were again mixed at a rate of 55.4 ml / mi by the simultaneous mixing method.
n at a flow rate of 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 60 ° C. and during re-simultaneous mixing with the solutions B1 and C1 was measured using the following solution D1. +8 each
mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH.
The seed emulsion 1 was obtained by immediately desalting and washing with water. This seed emulsion 1 has 90% of the total projected area of the silver halide grains.
The above results indicate that the hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 were formed, the average thickness of the hexagonal tabular grains was 0.064 μm, and the average grain size (circular diameter conversion) was 0.595 μm. It was confirmed with a microscope. The coefficient of variation of the thickness is 40
%, And the coefficient of variation of the distance between twin planes was 42%.

Solution A1 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml

Solution B1 2.5N silver nitrate aqueous solution 2825 ml Solution C1 potassium bromide 841 g water with 2825 ml solution D1 1.75 N potassium bromide aqueous solution

<Preparation of Tabular Silver Halide Emulsion Em-1> The following solution A2 was vigorously stirred in a reaction vessel at 60 ° C., and a part of the following solution B2 and the following solution C2 were added thereto.
And half of the following solution D2 were added by the double jet method over 5 minutes, and then the solution B2 and the solution C2 were successively added.
Is added over a period of 37 minutes, a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. Finally, the solution B2 and the solution C2 are added.
Was added over 33 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

After completion of the addition, the mixture was cooled to 40 ° C., subjected to ultrafiltration desalting by a known method, added with a 10% gelatin solution, stirred at 50 ° C. for 30 minutes, and redispersed. After redispersion 4
At 0 ° C., the pH was adjusted to 5.80 and the pAg to 8.06,
A tabular silver halide emulsion Em-1 was obtained.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.984 μm and the average thickness was 0.9 mm.
Tabular silver halide grains having a size of 22 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained. Also,
The average of the twin plane distance is 0.020 μm, and grains having a twin plane distance to thickness ratio of 5 or more are 97% (number) of all tabular silver halide grains and 10 or more grains are 49 or more. %, 15
These particles accounted for 17%.

Solution A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol solution) 2.25 ml Seed emulsion-1 1.722 mol equivalent Equivalent to 3150 ml with water. Solution B2 1734 g of potassium bromide Make up to 3644 ml with water. Solution C2 Silver nitrate 2478 g Make up to 4165 ml with water. Solution D2 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) (*) Equivalent to 0.080 mol

The fine grain emulsion comprising the silver iodide grains (average grain size: 0.05 μm) was prepared as follows.

5.0 containing 0.06 mol of potassium iodide
In 6.64 liters of an aqueous solution of gelatin in weight%, 7.06
Two liters of an aqueous solution containing mol silver nitrate and 2 liters of an aqueous solution containing 7.06 mol potassium iodide were added over 10 minutes. During the formation of the fine particles, the pH was adjusted to 2.0 using nitric acid.
And the temperature was controlled at 40 ° C. After the grain formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution to obtain a fine grain emulsion (*).

<Chemical Sensitization of Tabular Silver Halide Emulsion Em-1>
C., and the following sensitizing dyes (A) and (B) were added in the following amounts as a dispersion of solid fine particles, and then a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and A dispersion of phenylphosphine selenide was added, and after 30 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,3,3 is used as a stabilizer.
An appropriate amount of a, 7-tetrazaindene (TAI) was added.

The above additives and their amounts (per mole of silver) are shown below. Sensitizing dye (A) 0.6 mol Sensitizing dye (B) 0.006 mol Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.2 mg Stabilizer (TAI ) 500 mg of a solid particulate dispersion of a spectral sensitizing dye is disclosed in JP-A-5-297.
It was prepared by a method according to the method described in JP-A-496. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used at 3500 rpm.
m by stirring for 30-120 minutes.

Sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (3
-Sulfopropyl) oxacarbocyanine-sodium salt sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) Dispersion of azoimidazolocarbocyanine-sodium salt triphenylphosphine selenide 120 g of triphenylphosphine selenide at 50 ° C. in ethyl acetate 30 k
g, stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25% by weight aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a 10 cm diameter dissolver at 50 ° C. for 30 minutes at a peripheral speed of the dispersion blade of 40 m / sec. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by weight or less. Thereafter, this dispersion was diluted with pure water to make up to 80 kg, and a dispersion of triphenylphosphine selenide was obtained.

<Preparation of silver halide photographic light-sensitive material> A polyethylene terephthalate film base (thickness: 175 μm) for X-rays colored blue with a density of 0.15 was coated on both sides.
A support coated with a coating solution having the following first layer (crossover cut layer) composition was used.
A coating solution having a layer (silver halide emulsion layer) composition and a coating solution having a third layer (protective layer) composition described below are simultaneously coated in a predetermined coating amount as described below, and dried. Material samples Nos. 1 to 20 were obtained.

The attached amount is shown as an amount per 1 m ^{2 on} one side of the photosensitive material. The silver halide emulsion Em-1 was prepared so that the coated silver amount was 1.3 g / m ² on one side.

Composition of First Layer (Crossover Cut Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² Colloidal silica (average particle size 0.014 μm) 10 mg / m ²

Second Layer (Silver Halide Emulsion Layer) Composition The following various additives were added to the emulsion obtained above. Compound (G) 0.5 mg / m^Two 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m^Two t-butyl-catechol 130 mg / m^Two Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m^Two Styrene-maleic anhydride copolymer 80mg / m^Two Sodium polystyrene sulfonate 80mg / m^Two Trimethylolpropane 350mg / m^Two Diethylene glycol 50mg / m^Two Nitrophenyl-triphenyl-phosphonium chloride 20mg / m^Two Ammonium 1,3-dihydroxybenzene-4-sulfonate 100mg / m^Two Sodium 2-mercaptobenzimidazole-5-sulfonate 5mg / m^Two Compound (H) 0.5 mg / m^Two n-C _FourH₉OCH_TwoCH (OH) CH_TwoN (CH_TwoCOOH)_Two 35mg / m^Two Dextrin (average molecular weight 1000) 0.2 g / m^Two However, 0.8 g / m2 for gelatin^TwoLike to be
It was adjusted.

Third layer (protective layer) composition Gelatin 0.6 g / m ² Polymethyl methacrylate matting agent (area average particle size 7.0 μm) 50 mg / m ² 2,4-dichloro-6-hydroxy-1, 3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / m ² C ₉ F ₁₉ O ( _{CH 2 CH 2 O) 11 H} 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 15 H 2mg / m 2 C 8 F 17 SO 2 N- (C 3 H ₇₎ (C H ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1 mg / m ² Hardener described in Table 1 0.4 mmol / m ²

[0109]

Embedded image

[0110]

Embedded image

(Preparation of Developing Agent) The following operations (A) to
According to (D), tablets for development replenishment and tablets for replenishment for fixing were prepared as solid processing agents.

Operation (A) Preparation of Tablet A for Replenishment for Development As a developing agent, sodium erythorbate 13,000 g
Is ground to a mean particle size of 10 μm in a commercially available bantam mill. To this fine powder, 4877 g of sodium sulfite,
After adding 975 g of phenidone and 1635 g of DTPA, mixing in a mill for 30 minutes and granulating by adding 30 ml of water at room temperature for about 10 minutes in a commercially available stirring granulator, the granulated product is dried in a fluidized bed. The granules are dried at 40 ° C. for 2 hours to remove the moisture of the granules almost completely. 2167 g of D-mannitol was added to the granules thus prepared at 25 ° C,
Using a mixer in a room conditioned to 40% RH or less
After the mixture was uniformly mixed for 1 minute, the obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being set to 8.715 g, and 2500 tablets were obtained. A tablet A for development replenishment was prepared.

Operation (B) Preparation of tablet B for replenishment of development 19500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, 32 of sodium hydrogen carbonate
50 g, glutaraldehyde sulfite adduct 650 g, polyethylene glycol # 6000 or 1354 g of the polyhydric alcohol shown in Table 1 are ground and granulated in the same manner as in the operation (A). The amount of water added was 30.0 ml, and after granulation, 50 ° C
For 30 minutes to remove the moisture of the granules almost completely. The mixture thus obtained was compressed and tableted using the same tableting machine as above at a filling amount per tablet of 9.90 g to prepare 2500 tablets B for replenishment for development.

Operation (C) Preparation of Tablet C for Fixing Replenishment 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate were pulverized and granulated in the same manner as in operation (A). The amount of water to be added is 500 ml, and after granulation, the granulated material is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture obtained in this manner was filled with the above tableting machine at a filling amount of 8.214 per tablet.
g and compression tableting to prepare 2500 fixing supplementary tablets C.

Operation (D) Preparation of tablet D for fixing replenishment 186 g of boric acid, aluminum sulfate / 18-hydrate 6500
g, glacial acetic acid 1860 g, and sulfuric acid (50% by weight) 925 g are pulverized and granulated in the same manner as in the operation (操作). Water addition amount is 10
After the granulation, the mixture is dried at 50 ° C. for 30 minutes to remove the moisture of the granulated product almost completely. The mixture obtained in this manner was charged in a tableting machine with the filling amount per tablet of 4.
The tablet was compressed to 459 g and compression tableting was carried out to prepare 2500 fixing replenishing tablets D.

A developer having the following composition was prepared using the prepared tablet for replenishment. 330 ml of a starter having the following composition was added to 16.5 liters of the obtained developer having a pH of 10.70 to adjust the pH to 10.45.

<Composition of developer> Potassium carbonate 120.0 g / l Sodium erythorbate 40.0 g / l DTPA 5.0 g / l 1-phenyl-5-mercaptotetrazole 0.05 g / l Sodium hydrogen carbonate 20.0 g / l Phenidone 3.0 g / l Sodium sulfite 15.0 g / l D-mannitol 15.0 g / l Glutaraldehyde sulfite adduct 4.0 g / l

<Developer Starter> 210 g of glacial acetic acid, K
Water obtained by adding water to 530 g of Br.

A fixing solution having the following composition was prepared using the above fixing replenishing tablet, and was used as a starting solution.

<Composition of Fixing Solution> Ammonium thiosulfate 160.0 g / l Sodium sulfite 12.0 g / l boric acid 1.0 g / l sodium hydroxide 5.0 g / l glacial acetic acid 10.0 g / l aluminum sulfate / 18-hydrate 35 0.0 g / l sulfuric acid (50% by weight) 5.0 g / l disodium ethylenediaminetetraacetate dihydrate 0.02 g / l

<Evaluation of Sample> (1) Evaluation of Silver Tone Each of the obtained film samples was subjected to two fluorescent intensifying screens (S
RO-250), irradiate with X-rays so that the concentration becomes 1.2 ± 0.5, modify the SRX-502 automatic developing machine so as to have the following processing time, and process using the above processing agent. And visually evaluated according to the following evaluation criteria.

At this time, the replenishment rate of the processing solution was 90 ml / m ^{2 for} both the developing solution and the fixing solution.

Evaluation Criteria A: Pure black B: Slightly yellowish C: Yellowish

(2) Evaluation of Unevenness of Gloss The obtained film sample was irradiated with X-rays in the same manner as in the evaluation of silver tone, developed, and visually evaluated according to the following evaluation criteria. (Evaluation criteria) A: There is almost no unevenness in gloss.

B: There is a little unevenness in gloss, but it can withstand visual perception.

C: There is considerable unevenness in gloss, and the image cannot be perceived visually.

(3) Evaluation of Drying Property A sample of a quarter size (25.4 × 30.2 cm) was
X-ray irradiation is performed in the same manner as in the evaluation of the silver tone, and the processing is continuously performed so that the short side is in the transport direction of the processing by the above-described development processing method. Sensory evaluation was performed by touch.

However, assuming that the silver halide photographic light-sensitive material is stored in a high-temperature and high-humidity place, a temperature of 30.degree.
% RH was evaluated. (Evaluation Criteria) A: The sample is completely dry even on the 30th sheet. B: The sample feels slightly cold when touching it on the 30th sheet, but there is no sticking between continuously processed samples, and it is a practically acceptable level. C: It is clear when touching the sample on the 30th sheet. Wet to In some cases, the continuously processed samples stuck together, and the results obtained at a level that was not practically used are shown in Table 2.

[0129]

[Table 2]

As is clear from Table 2, according to the processing method of the present invention, the silver tone and the drying property are good, and the gloss unevenness is small.

[0131]

According to the method for processing a silver halide photographic light-sensitive material of the present invention, an excellent silver color tone can be obtained, drying properties are excellent and gloss unevenness is reduced even when processing is performed quickly. Can be.

Claims (2)

[Claims] 1. A hydrophilic composition comprising a silver halide emulsion layer on a support.
Silver halide photographic light-sensitive material provided with a hydrophilic colloid layer
Processing method of silver halide photographic material processed with developer
, A hydrophilic colloid layer containing a silver halide emulsion layer
Wherein at least one layer of the following is a hardener represented by the following general formula (1)
And the developer is 5-20 carbon atoms, water
It is a developer containing a saccharide having 5 to 20 acid groups.
A method for processing a silver halide photographic light-sensitive material. Embedded image[Wherein, R¹ , R^Two Represents a hydrogen atom, an alkyl group, an aryl
Group or R¹ , R^Two Are bonded to each other and
Represents a group forming an elementary ring. R^Three Represents a substituent. m is
0 to 5, and when m is 2 or more, a plurality of R^Three Is the same
Or different from each other. 1 is 0 or 1
Represents X is the ion required to offset the molecular charge
Represents n is the number required to neutralize the total charge of the molecule
Represents However, it is 0 when an inner salt is formed.
You. ] 2. The method for processing a silver halide photographic material according to claim 1, wherein the developer is a developer containing reductones.